Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
  • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
  • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen

Definitions

• This invention relates to a hydrophilic curable resin composition for coating. More particularly, the invention relates to the resin composition which can be cured by the irradiation of heat, actinic rays or ionizing radiation, or the addition of hardener, where the obtained coating therefrom is extremely hydrophilic even after the curing, while such coating has excellent water resisting property.
• hydrophilic resin compositions for coatings are well known.
• ionic hydrophilic resin which contains, as a part of the copolymerizable material, anionic polymerizable monomers such as acrylic acid and 2-sulfoethyl methacrylate or cationic polymerizable monomers such as vinylpyridine and vinylbenzyl quaternary ammonium salt.
• the hydrophilic resin composition can be obtained also by copolymerizing nonionic hydrophilic monomers such as 2-hydroxyethyl methacrylate, polyethylene glycol monomethacrylate and hydroxypropyl methacrylate, as at least one component.
• polyethyleneglycol and the like can be used in order to impart the hydrophilic property to polyester and to form a polyether ester.
• the hydrophilic groups are contained as side chains and cross-linkages are scarcely produced, so that the formed coating film is susceptible to chemical actions and is subject to hydrolysis, thereby showing poor water resistance.
• the large part of the main chain of the polymer is consisting of ethylenic sequence of carbon atoms, thus the obtained coating is not always satisfactory in flexibility and unsuitable for the use where high flexibility is required.
• the hydrophilic property thereof is not so large, thus even though is can be used merely as the water soluble resin composition, it may be difficult to be employed as the hydrophilic coating composition having a good water resistance.
• the conventional polyether ester it is the same as the above that it does not form three dimensional structure, and by the existence of polyether portions at the terminals of the molecule, the polymer is inferior not only in the water resistance but also in other several properties such as friction resistance, weather resistance and solvent resistance, therefore, it can not be used widely for the purpose of giving hydrophilic property.
• polyether derivatives having cross linking functional groups such as epoxy group at both ends of the molecule, however in these case, the density of cross linkage is low, therefore the superior water resistance can not be expected.
• the hydrophilic resin composition for coating of the present invention is novel and quite different from the above-mentioned conventional hydrophilic resin compositions.
• the hydrophilic resin composition of the present invention comprises polyether ester as the main component, which is modified with ethylenically unsaturated groups, and contains 40 to 90 % by weight of polyether portion in the main chain of the molecule, at the same time, 3 equivalents or more of polymerizable ethylenically unsaturated bond component per 1 mole of the number average molecular weight are contained.
• the present invention relates to hydrophilic curable resin composition for coating which comprises ethylenically unsaturated and hydrophilic resin component consisting of linear hydrophilic polyester structure and 3 or more equivalents of polymerizable ethylenically unsaturated groups per 1 mole of said ethylenically unsaturated and hydrophilic resin, and said ethylenically unsaturated and hydrophilic resin having number average molecular weight within a range from 2,000 to 10,000 and being formed by either of methods consisting of
• R' represents a hydrogen atom or a methyl group and n represents a positive integer from 6 to 50, inclusive, and used in an amount such that 40 to 90 weight percent of said ethylenically unsaturated and hydrophilic resin is consisting of said polyalkylene glycol portion, and benzene polycarboxylic acids selected from the group comprising trimellitic acid, trimellitic anhydride, hemimellitic acid, pyromellitic acid pyromellitic anhydride and benzenepentacarboxylic acid, and said ethylenically unsaturated compounds containing oxirane oxygen being selected from the group comprising glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether,
• linear hydrophilic carboxylated polyester having free carboxyl group at the terminal of linear hydrophilic polyester structure is made to react upon ethylenically unsaturated compounds containing oxirane oxygen, said linear hydrophilic carboxylated polyester being formed by polycondensation of dialcohols comprising polyalkyleneglycol expressed by the formula
• R' represents a hydrogen atom or a methyl group and n represents a positive integer from 6 to 50, inclusive, and used in an amount such that 40 to 90 weight percent of said ethylenically unsaturated and hydrophilic resin is consisting of said polyalkyleneglycol portion, and 2 to 4 valent polycarboxylic acid in an amount such that a free carboxyl group or groups are left at the terminal of said linear hydrophilic polyester structure, and said ethylenically unsaturated compounds containing oxirane oxygen being selected from the group comprising glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether,
• linear hydrophilic carboxylated polyester having free carboxyl group pendent from said linear hydrophilic polyester structure is made to react upon ethylenically unsaturated compounds containing oxirane oxygen, said linear hydrophilic carboxylated polyester being formed by polycondensation of dialcohols comprising polyalkyleneglycol and carboxylated dialcohol, said polyalkyleneglycol being expressed by the formula
• R' represents a hydrogen atom or a methyl group and n represents a positive integer from 6 to 50, inclusive, and used in an amount such that 40 to 90 weight percent of said ethylenically unsaturated and hydrophilic resin is consisting of said polyalkyleneglycol portion
• said carboxylated dialcohols being selected from the group comprising ⁇ , ⁇ -dihydroxymethyl propionic acid and tartaric acid, with divalent carboxylic acids or acid anhydrides and said ethylenically unsaturated compounds containing oxirane oxygen being selected from the group comprising glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether, and
• R' represents a hydrogen atom or a methyl group and n represents a positive integer from 6 to 50, inclusive, and used in an amount that 40 to 90 weight percent of said ethylenically unsaturated and hydrophilic resin is consisting of said polyalkyleneglycol portion
• said tri- and tetravalent polyalcohol being selected from the group comprising glycerol, trimethyolethane, trimethylolpropane and pentaerithritol, with divalent carboxylic acids or acid anhydrides
• said ethylenically unsaturated isocyanate compounds being formed by reaction of ethylenically unsaturated monomer containing hydroxyl group selected from the group comprising 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and allyl alcohol upon di- and/or triisocyanate compound selected from the group comprising tolylene diisocyanate
• polyether portion denotes that atomic group having a chemical formula --O--CH 2 --CHR--O n in which R represents a hydrogen atom or a methyl group and n represents a positive integer from 6 to 50.
• hydrophobic portion denotes the parts of the molecule of polyether ester other than said polyether portion.
• the obtained film has the excellent hydrophilic property by the existence of a relatively large proportion of said polyether portion, it has also superior water resistance, in addition to that other several properties such as flexibility, friction resistance, weather resistance and solvent resistance of the cured film in the present invention are all excellent. Accordingly, the coating film obtained in the present invention has a wide variety of usages.
• the characteristic features of the hydrophilic resin used for the composition of the present invention are that it contains considerably large proportion of the hydrophilic polyether structure in the range of 40 to 90 % by weight, and that the remaining non-hydrophilic portion contains the polymerizable ethylenically unsaturated bond component.
• the polymer for example, polyethylene glycol
• the polymer consists of hydrophilic polyether portion and non-hydrophilic portion forming a water-resistant resin consisting of polymerizable ethylenically unsaturated bond component and the ratio of them is in a suitable range
• the polyether component exists in a ratio of 40 to 65 % by weight
• the polymer shows the property of polymeric surface active agent, and it is suitable for imparting the hydrophilic property to the surface of the coated articles.
• the polymerizable component exists in the non-hydrophilic portion of the polymer in a large degree and a dense three dimensional structure is formed in the resulting film, therefore the content of the polyether component can be increased, for example as high as 90 % by weight, which value is very high as compared with the conventionally known polyether esters.
• the hydrophilic portion and the non hydrophilic portion in a certain arrangement and in layered construction in the molecule, even when the ratio of non-hydrophilic portion is very small, such portion can be polymerized, and the connections between the non-hydrophilic portions are formed by covalent bonds which are far stronger than the secondary bonds such as van der Waals' bond, thereby the surface active property can be exhibited. Accordingly, it is possible not only that the ratio of hydrophilic portion can be increased as compared with the prior ones, but also that several properties of the product can be extremely improved by the provision of the network structure of the polymer molecule.
• hydrophilic resin of the present invention Another characteristic feature of the hydrophilic resin of the present invention is that the hydrophilic polyether portion is contained in the polymer as a part of the main chain thereof. So that, water molecules are adsorbed along the polyether portion and contained in the network structure, while the polymer is not attacked by water because the cross linkage portions of the molecule are hydrophobic, therefore, the hydrophilic resin of the invention is chemically stable and water resistance and alkali resistance are good enough.
• the hydrophilic resin composition for coating of the present invention has various excellent characteristics as being mentioned in the above, therefore it can be used for the coatings of various articles used for several purposes.
• the condensed water can be flowed down as a water film by the application of the coating according to the present invention to the glass or other surfaces, so that such troubles can be prevented.
• the coatings of the present invention are excellent antistatic agents, therefore if electrically insulating polymer articles in various configurations are coated with using the composition of the present invention, the attraction of light materials such as paper, the inconvenience and discomfort by the electric shock, the dirt by the attracted dust from the surrounding air and the danger of fire by electric discharge to inflammable material can be prevented by the elimination of the static electricity.
• the hydrophilic resin composition of the invention contains, as the principal component, polyether ester having polymerizable unsaturated bond component, and more particularly, the composition contains the resinous material consisting of 40 to 90 % by weight of polyether which is represented by the following general formula:
• R' is a hydrogen atom or a methyl group
• n is an integer from 6 to 50, inclusive, and 60 to 10 % by weight of the residual non-hydrophilic portion comprising arylene groups and/or alkylene groups, and if desired, of polymerizable alkenylene group which portion contain 3 equivalents or more of polymerizable ethylenically unsaturated bond component as substituent groups or as side chains or terminal groups per mole of the average molecular weight of the resinous material. If the amount of said polymerizable ethylenically unsaturated bond component is less than 3 equivalents per 1 mole of the number average molecular weight of the resin, the curability of the resin is not sufficient. Further, the compounds in which polymerizable ethylenically unsaturated bond component in which polymerizable ethylenically unsaturated bond component is connected to the main chain by way of urethane bond are included in the above definition.
• arylene group is meant an aromatic hydrocarbon in which two hydrogen atoms thereof are removed and the reactivity with other atoms or atomic groups is given at that position.
• alkylene group is meant a group which is obtained by removing two hydrogen atoms from the different carbon atoms of a saturated hydrocarbon being represented by the general formula, C n H 2n +2 , in which n is a positive integer generally not more than 30.
• alkenylene group is meant a group which is obtained by removing two hydrogen atoms from an unsaturated hydrocarbon having a double bond being represented by the general formula, C n H 2n , in which n is a positive integer generally 2 or 3.
• arylene group and alkylene group which may be added with the polymerizable ethylenically unsaturated bond component as the substituent group
• the combinations of them such as alkylarylene group and arylalkylene group can be used also for the composition of the present invention.
• Aromatic polycarboxylic acid can be used for introducing the ethylenically unsaturated bond component to the terminal of the polymer molecule, further it can be used as the intermediate component in the molecule only for the purpose of elongating the length of molecular chain in case the unsaturated bond component is not so much necessary according to the property of the composition to be obtained.
• aromatic polycarboxylic acid those which are useful in the process are phthalic acid anhydride, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acids, 1,2,3-benzene tricarboxylic acid (hemimellitic acid), 1,2,4-benzene tricarboxylic acid (trimellitic acid), trimellitic anhydride, 1,3,5-benzene tricarboxylic acid (trimesic acid), 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid), pyromellitic anhydride and benzene pentacarboxylic acid.
• phthalic acid anhydride 1,2,3-benzene tricarboxylic acid (hemimellitic acid), 1,2,4-benzene tricarboxylic acid (trimellitic acid), trimellitic anhydride, 1,3,5-benzene tricarboxylic acid (trimesic acid), 1,2,4,5-benzene tetrac
• the raw materials for preparing the compounds having alkylene groups are aliphatic compounds which have 2 or more of functional carboxylic groups, there are for example, adipic acid, succinic acid, succinic anhydride, and their alkyl derivatives, malonic acid, hydroxysuccinic acid, tartaric acid, ⁇ , ⁇ -dihydroxymethyl propionic acid ( ⁇ , ⁇ -dimethylol propionic acid) and citric acid.
• polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylol ethane, trimethylol propane, glycerol and pentaerythritol can be used.
• ⁇ , ⁇ -unsaturated dicarboxylic acids and their anhydrides for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and citraconic anhydride can be used.
• the advantage of the employment of the acid anhydrides in place of polycarboxylic acid as the raw materials for the formations of arylene group, alkylene group and alkenylene group comes from the fact that when the ester bonds are formed through the reaction with hydroxyl groups at the terminals of polyether and other alcohol components, it is not necessary to carry out the reaction at a high temperature which is different from the formation of ester bonds by the dehydration condensation, thereby the ratio of selectivity between the formation of ester bonds by the ring opening of the acid anhydrides and those by dehydration of carboxyl groups become large, accordingly, the polymolecularity of the polymer is lowered and the uniform composite can be obtained.
• the oxirane ring forms ester bond in the presence of the carboxyl group by the ring opening through heating at a relatively low temperature or ar the room temperature without the fear of viscosity increase or gelation by the thermal polymerization between unsaturated bonds, thereby the introduction of polymerizable substituent group by ester bond can be accomplished.
• the compounds having both of the ethylenically unsaturated bond component and the oxirane ring which can be used for the above purpose, there are, for example, glycidyl acrylate, glycidyl methacrylate, and acrylgrycidyl ether.
• polyisocyanates can be used as another method for joining the polymerizable ethylenically unsaturated bond component. That is, the isocyanate group forms an urethane bond by the reaction with a hydroxyl group at the room temperature or at a relatively low temperature, therefore ethylenically unsaturated compound having isocyanate group can be used for this purpose, in which the ethylenically unsaturated bond can be connected without the fear of thermal polymerization by the unsaturated bond during the reaction.
• the isocyanate compound containing ethylenically unsaturated component used for this purpose is, for example, an adduct which is prepared by adding an ethylenically unsaturated compound having hydroxyl group to di- or triisocyanate so as to leave 1 equivalent of the isocyanate group unreacted per 1 mole of said isocyanate compound.
• di- or triisocyanates for example, there are tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Desmodur L (Tradename of Wegriken Bayer A.G., Germany, H 5 C 2 C(CH 2 OCONHC 6 H 3 CH 3 NCO) 3 and Desmodur N (The same as the above, OCN(CH 2 ) 6 N [CONH(CH.sub. 2) 6 NCO] 2 .
• ethylenically unsaturated compounds having hydroxyl group it is generally convenient to use the following compounds, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl methacrylates, hydroxypropyl acrylates and allyl alcohol.
• the resinous material of the invention is prepared from the combination of one or more of materials for arylene group, alkylene group or alkenylene group and compounds containing polymerizable ethyleneically unsaturated bond component, and polyethers such as polyethylene glycol and polypropylene glycol.
• the applicable weight ratio of the above materials is such that the hydrophilic component of polyether forms 40 to 90 % by weight, preferably 50 to 80 % by weight, of the resin and the other non-hydrophilic component forms 60 to 10 % by weight, preferably 50 to 20 % by weight of the resin.
• the ratio of hydrophilic component is less than 40 % by weight or more than 90 % by weight, and that of the non-hydrophilic component is more than 60 % by weight or less than 10 % by weight, the surface activity of the obtained resinous material is not sufficient, thereby the excellent effects as those of the hydrophilic resin composition of the present invention can not be expected.
• the obtained resinous material has the number average molecular weight of 2,000 to 10,000 to give a wide usage, however, it does not always follow for special uses.
• X is a non-hydrophilic atomic group such as arylene group having branched structure with or without substituent groups
• Y is an atomic group having polymerizable ethylenically unsaturated bond
• Z is a hydrophilic atomic group consisting of polyester, and each of them is not always a single kind, that is each of them may be a mixture of the above-mentioned materials.
• the above X can be a polymerizable alkenylene group, and in such case, it is not necessary to join the ethylenically unsaturated group by branched structure.
• 1 and m are 0 (zero) or integers from 1 to 3, and each of them of generally 1 or 2, further they are not necessarily the same numerals in the same molecule.
• n is 0 or positive integer and is generally not more than 20. Further, the sum of 1 and m in the same molecule is 3 or more. Accordingly, the case in which X is arylene group, alkylene group or alkenylene group having a substituent other than the ethylenically unsaturated bond component is included.
• X is not restricted to arylene group, alkylene group or alkenylene group, and X itself is a high polymer such as polyester and having a branched structure or alkenylene group as a part thereof, the effect of the present invention can be expected equally.
• the proportion of said polymerizable ethylenically unsaturated bond component is 3 equivalents or more against 1 mole of the number average molecular weight of the polymer. If the proportion is less than 3 equivalents, the polymerizing property of the hydrophilic resin composition is decreased, so that any special effect on the hydrophilic property can not be obtained as compared with the known hydrophilic compositions. There is no upper limit of said proportion, however, if it is contained in an excessively large amount, the stability of the composition during the production process and storage is liable to decrease, therefore, it is preferably stabilized by adding with a polymerization inhibitor or a stabilizer.
• the hydrophilic resin composition of the present invention can be easily prepared from the above-mentioned materials. That is, in the first step, the intermediate material of polyether ester is produced by using polyethyleneglycol or polypropyleneglycol and, if necessary, tri- or polyfunctional aromatic or aliphatic compounds as the source of the branched structure. This reaction can be carried out according to the conventional methods which are well known in the technical field of the invention concerned. That is, polyethers such as polyethyleneglycol may be mixed with the other raw materials and heated at an appropriate temperature.
• the residual carboxyl group or hydroxyl group in the polyether ester molecule as obtained in the first step is added with the polymerizable ethylenically unsaturated bond component.
• the compounds containing oxirane ring are used as the unsaturated bond components to be connected to carboxyl group, thus the reaction with the carboxyl group can be carried out very easily, therefore high temperature heating is not necessary, and the reaction can be carried out even at room temperature, preferably by heating between 50 to 80°C. Further, when an unsaturated urethane compound is joined with the hydroxyl group, high temperature heating is not necessary too, and such reaction can be carried out at room temperature or preferably at a temperature of 50° to 80°C.
• the known polymerization inhibitor such as hydroquinone and benzoquinone may be added previously in an amount not exceeding 2g per 1 equivalent of said ethylenically unsaturated bond components. If the amount exceeds 2 g per 1 equivalent of said ethylenically unsaturated bond components, the curing of the composition is obstructed.
• each of the above step can be carried out in the presence of solvents which are inactive to the esterification or urethanation, for example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, or the polar solvents of volatile ethers such as dioxane and tetrahydrofuran.
• solvents which are inactive to the esterification or urethanation for example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, or the polar solvents of volatile ethers such as dioxane and tetrahydrofuran.
• the nonpolar hydrocarbon solvents such as toluene and xylene can be used together as far as they are not obstructive in view of the solubility.
• hydrophilic resin composition is applied on the surfaces of several articles as it is, or concentrated, or diluted previously with a miscible solvent.
• the method of the application of the composition may be selected from the well known ones such as spraying, dipping, flowing, roller coating and so forth.
• the volatile solvent is vaporized, and followed with the curing treatment.
• the applicable curing methods there are, for example, heating, irradiation of actinic rays and irradiation of ionizing radiation.
• the polymerization initiators for example, ⁇ , ⁇ -azobisisobutyronitrile, benzoyl peroxide and cumene hydroperoxide can be used, and the amount of addition thereof may be 0.1 to 6 % by weight against the resinous content of the composition. If the amount is less than 0.1 % by weight against the resinous content, the heat-curability of the resin is lowered, and, if the amount exceeds 6 % by weight, the storage stability of the composition is injured while the heat-curability is not fortified.
• the most suitable conditions for the heating are in the range of a temperature from 80° to 200° C, and a duration from 0.5 to 30 minutes, and the heating can be carried out in any of air, inert gases, water vapor and vacuum.
• the composition may be preferably added with a photosensitizer before the coating.
• a photosensitizer any of compatible organic ones, for example, those selected from the group comprising tetramethyldiaminobenzophenone, benzoin, N.N-dibutyl-p-nitrosoaniline, benzoin methyl ether, benzoin ethyl ether, ⁇ -methylbenzoin, ⁇ -phenyl benzoin diacetyl, 1-naphthalene solfonylchloride, ⁇ -bromoacetophenone, eosine and erithrosine, may be used, and as for the light sources, any of the sources which produce the rays of 250 to 600 mu may be used.
• the appropriate amount of the photosensitizer to be added is 0.1 to 3 % by weight of the resin in the composition. If the amount of the photosensitizer to be added is less than 0.1 % by weight of the resin in the composition, the photo-curability of the resin does not distinguish, and if the amount exceeds 3 % by weight of the resin, the durability of the cured coating film is worse while the photo-curability of the resin is almost the same as the composition containing 3 % by weight of photosensitizer. Further, ionizing radiations such as electron beam and gamma rays can be used for the curing of the composition, and the dosage of irradiation thereof may be 0.1 to 20 Mrad.
• reaction system was cooled to about 65°C, and 228 g (1.6 moles) of glycidyl methacrylate and 1 g of hydroquinone were added, further about 450 g of tetrahydrofuran was slowly added drop by drop with temperature regulation, thereby the reaction was continued at about 70° to 75°C with boiling and reflux. After 4 hours continuation of this heating, the acid value of the resinous component became about 3.5.
• This resin solution was cooled as it is to obtain the hydrophilic resin composition for coating.
• the resin content of this solution was about 60 %.
• the ratio of polyether portion in this hydrophilic resin was about 58 % by weight.
• the content of non-volatile matter of the obtained hydrophilic resin composition was about 85 %, and the acid value of non-volatile matter was 7.3.
• the ratio of polyether portion in the hydrophilic resin of this Example was about 68 % by weight.
• This reaction mixture was cooled to 80°C and was added with 115 g (0.6 mole) of trimellitic anhydride, 160 g (0.6 mole) of dodecylsuccinic anhydride (made by Teikoku Kako Kabushiki Kaisha, Japan; trade name: DSA), and 240 g of methyl ethyl ketone, and the above acid anyhydrides were joined with said polyether ester by the reaction at 90° to 100°C for 5 hours.
• the above reaction product was added with 230 g (1.8 moles) of glycidyl acrylate and 1.8 g of hydroquinone, and caused to react at 60° to 70°C for 4 hours, thereby the unsaturated bond was added.
• the hydrophilic resin composition of about 82 % in the resin content and 3.2 in the acid value of resinous component was obtained.
• the ratio of polyether portion of this hydrophilic resin composition was about 55 % by weight.
• the above reaction mixture was cooled to 60° to 70°C and was added with 240 g of dioxane, and 183 g of unsaturated urethane adduct which was prepared by the undermentioned method was then added little by little to the above mixture. After this addition, the mixture was kept at the same temperature for 5 hours to obtain the unsaturated hydrophilic resin, thereby the composition of 82 % in the resin content was obtained.
• the ratio of polyether portion in this modified hydrophilic resin was about 72 %.
• a 1 liter four neck flask with a reflux condenser, a thermometer, a dropping funnel and a stirrer was fed with 344 g (2 moles) of tolylene diisocyanate and heated at about 60°C by a water bath, while 282 g (2.2 moles) of 2-hydroxyethyl methacrylate containing 2 g of benzoquinone was dropped slowly for about 1.5 hours from the dropping funnel.
• the temperature was always regulated at 60° to 70°C, and after the above dropping, the reaction was completed by keeping the reaction mixture at the same temperature for further 3 hours, thereby a solid unsaturated urethane adduct was obtained.
• the ratio of polyether portion of the hydrophilic resin of this Example was about 51 % by weight.
• the reaction vessel as used in Preparation Example 1 was fed with 1,500 g (1 mole) of polyethylene glycol (number average molecular weight: 1500), 175 g (0.8 mole) of pyromellitic anhydride and 300 g of dioxane, and heated at 90° to 100°C for 5 hours. Thereby polyether ester was prepared by the ring opening of the acid anhydride.
• reaction mixture was diluted with 300 g of methyl ethyl ketone, and further added with 228 g (1.6 moles) of glycidyl methacrylate and 2 g of hydroquinone, then heated at 70° to 80°C for 5 hours to cause the addition reaction, thereby the hydrophilic resin composition was obtained.
• the ratio of polyether portion in this hydrophilic resin was about 78 % by weight.
• the reaction vessel as used in Preparation Example 1 was fed with 750 g (1.5 moles) of polyethylene glycol (number average molecular weight: 500), 218 g (1 mole) of pyromellitic anhydride and 300 g of dioxane, and heated at 90° to 100°C for 5 hours to obtain the polyether ester.
• this reaction mixture was added with 456 g (4 moles) of acrylglycidyl ether and 2 g of hydroquinone, and was caused to react at 80° to 90°C for 4 hours to obtain the hydrophilic resin composition.
• the ratio of polyether portion in this hydrophilic resin was about 45 % by weight.
• a 2 liter four neck flask with an inert gas inlet pipe, a reflux condenser, a thermometer and a stirrer was fed with 480 g of 2-hydroxyethyl methacrylate, 20 g of ethylene glycol dimethacrylate, 400 g of ethyl alcohol, 200 g of ethylene glycol monoethyl ether (cellosolve) and 5 g of ⁇ , ⁇ -azobisisobutyronitrile, then the mixture was heated to polymerize at 78° to 79°C for 5 hours in the presence of nitrogen gas flow. After the polymerization, the reaction mixture was diluted and cooled with 1800 g of water, 1,400 g of ethyl alcohol and 700 g of Cellosolve to obtain Comparative Composition 1.
• the ratio of polyether portion of the resin of this Composition was about 26 % by weight.
• hydrophilic resin compositions as obtained in Preparation Examples 1, 2, 3 and 6 were added with ⁇ , ⁇ -azobisisobutyronitrile in the amount of 3 % by weight against the resinous solid contents of the compositions, respectively. Then the viscosities of the compositions were adjusted by additions of methyl ethyl ketone so as to facilitate the coating operation, and each of thus prepared composition was applied on one side surface of a mild steel plate of 0.8 mm in thickness so as to form a coating of 5 to 8 microns in dried thickness. After the evaporation of the solvent, each of the test plates were heated at 150°C for 10 minutes, thereby the applied films were cured.
• each of the test plates was immersed into water at 20°C for 48 hours and 0.5 % aqueous caustic soda for 24 hours, however, any change was not found with regard to the coatings obtained from the composition of the present invention.
• the coating film which was obtained from said Comparative Composition 2 was partially dissolved by the immersion into the 0.5 % aqueous caustic soda.
• the hydrophilic resin composition as obtained in Preparation Example 4 was added with benzoin ethyl ether in the amount of 2 % by weight against the resinous solid content of the composition, then the viscosity of the composition was adjusted by methyl ethyl ketone to facilitate the use. Thereafter, thus obtained composition was applied on one side surface of a polished glass plate of 2 mm in thickness so as to form a dried coating film of about 20 microns thickness. After the evaporation of the solvent, the applied film was cured by irradiation of ultraviolet rays for 8 minutes from a chemical lamp (made by Tokyo Shibaura Electric Co., Ltd., Japan; Model: SL-20BL) which is placed at 20 cm distance.
• a chemical lamp made by Tokyo Shibaura Electric Co., Ltd., Japan; Model: SL-20BL
• the hydrophilic resin composition as obtained in Preparation Example 5 was applied on one side surface of 20 cm ⁇ 30 cm ABS (acrylonitrile-butadiene-styrene) resin plate of 3 mm in thickness so as to form a dried layer of about 10 microns thickness, and the formed layer was applied with about 8 Mrad dose of 300 KeV electron beam to be cured.
• ABS acrylonitrile-butadiene-styrene
• this test plate was rubbed strongly with dried paper and fabric of polyester fiber, however any electric charge was not observed.
• hydrophilic resin composition of each Example as indicated in the following Table with or without curing agent was added with methyl ethyl ketone, thereby the viscosity of the composition was adjusted to facilitate the coating operation.
• Said composition was then applied to one side of transparent polyester film on the market of 100 microns in thickness so as to form a coating layer of 17 to 23 microns in dried thickness by using bar coater. After evaporating the solvent at the room temperature, each coating layer was cured through the method and condition as indicated in the following Table. While, the test piece was weighed before and after the coating.
• test piece was then immersed into distilled water at 60°C for 30 minutes, thereafter the test piece was taken out from water and the water on the surface was wiped off. And immediately thereafter, the test piece was weighed to obtain the quantity of water which is absorbed in the coating film.
• the rate of absorption as indicated in the Table was calculated from the following equation. ##EQU3##
• the adhesion between the polyester film and the coating film is very excellent, the changes of appearance such as blistering and peeling after the immersion were not observed, and any crack and peeling were not caused even when the coated film was folded.
• the coating film which is obtained from the composition of the present invention is excellent.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polyesters Or Polycarbonates (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Polyethers (AREA)
• Polyurethanes Or Polyureas (AREA)
• Paints Or Removers (AREA)

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Citations (16)

• 1971
  • 1971-12-03 JP JP9717671A patent/JPS5328936B2/ja not_active Expired
• 1972
  • 1972-11-30 US US05/310,822 patent/US3932356A/en not_active Expired - Lifetime
  • 1972-12-01 FR FR7242857A patent/FR2162179B1/fr not_active Expired
  • 1972-12-01 GB GB5571772A patent/GB1418884A/en not_active Expired
  • 1972-12-02 DE DE2259109A patent/DE2259109A1/de active Pending
• 1973
  • 1973-08-20 FR FR7330163A patent/FR2185054B1/fr not_active Expired

Patent Citations (16)

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